Exploring the effect of pressure on the crystal structure and caloric properties of the molecular ionic hybrid [(CH)NOH][CoCl].

The hybrid metal halide [(CH)NOH]CoCl exhibits a first-order phase transition at ∼ 343 K. Its crystal structure and caloric properties respond significantly to moderate pressures (1-1000 bar), demonstrating potential for applications in emerging solid-state refrigeration technologies.

Empowering CO Eco-Refrigeration With Colossal Breathing-Caloric-Like Effects in MOF-508b.

Today, ≈20% of the electric consumption is devoted to refrigeration; while, ≈50% of the final energy is dedicated to heating applications. In this scenario, many cooling devices and heat-pumps are transitioning toward the use of CO as an eco-friendly refrigerant, favoring carbon circular economy. Nevertheless, CO still has some limitations, such as large operating pressures (70-150 bar) and a critical point at 31 °C, which compromises efficiency and increases technological complexity.

Order-disorder phase transition and molecular dynamics in the hybrid perovskite [(CH)NH][Mn(N)].

We present a temperature-dependent Raman scattering study of a [(CH)NH][Mn(N)] hybrid organic-inorganic azide-perovskite, in which we have analysed in detail the wavenumber and full width at half-maximum (FWHM) of lattice modes and internal modes of the NC skeleton, N and CH molecular groups. In general, the modes exhibited unusual behaviour during the phase transitions, including discontinuity in the phonon wavenumber, bandwidth, and unconventional shifts upon temperature variation. Spectral features on heating reveal the absence of significant distortions in the NC skeleton and a relatively restricted order-disorder process of the TrMA cations.

Discovery of Colossal Breathing-Caloric Effect under Low Applied Pressure in the Hybrid Organic-Inorganic MIL-53(Al) Material.

In this work, "breathing-caloric" effect is introduced as a new term to define very large thermal changes that arise from the combination of structural changes and gas adsorption processes occurring during breathing transitions. In regard to cooling and heating applications, this innovative caloric effect appears under very low working pressures and in a wide operating temperature range. This phenomenon, whose origin is analyzed in depth, is observed and reported here for the first time in the porous hybrid organic-inorganic MIL-53(Al) material.

Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH)N][Cd(N)].

Temperature-dependent Raman scattering and differential scanning calorimetry were applied to the study of the hybrid organic-inorganic azide-perovskite [(CH)N][Cd(N)], a compound with multiple structural phase transitions as a function of temperature. A significant entropy variation was observed associated to such phase transitions, |∆S| ~ 62.09 J·kg K, together with both a positive high barocaloric (BC) coefficient |δT/δP| ~ 12.

[(CH)NH]PbX (X = Cl and Br), 2D-Perovskite Related Hybrids with Dielectric Transitions and Broadband Photoluminiscent Emission.

We have prepared two new lead halides with the novel general formula of DMAPbX (DMA = [(CH)NH] and X = Cl or Br) by using an easy route under mild conditions at room temperature. These compounds exhibit an unprecedented crystal structure, are formed by layers of distorted [PbX] octahedra, which share corners and faces, and contain intercalated DMA cations. Very interestingly, they display dielectric transitions, which are related to a partial order-disorder process of the DMA cations between 160 and 260 K.

Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH3 )4 N][Mn(N3 )3 ] with Perovskite-Like Structure.

The perovskite azido compound [(CH3 )4 N][Mn(N3 )3 ], which undergoes a first-order phase change at Tt =310 K with an associated magnetic bistability, was revisited in the search for additional ferroic orders. The driving force for such structural transition is multifold and involves a peculiar cooperative rotation of the [MnN6 ] octahedral as well as order/disorder and off-center shifts of the [(CH3 )4 N](+) cations and bridging azide ligands, which also bend and change their coordination mode. According to DFT calculations the latter two give rise to the appearance of electric dipoles in the low-temperature (LT) polymorph, the polarization of which nevertheless cancels out due to their antiparallel alignment in the crystal.

Magnetic Ordering-Induced Multiferroic Behavior in [CH3NH3][Co(HCOO)3] Metal-Organic Framework.

We present the first example of magnetic ordering-induced multiferroic behavior in a metal-organic framework magnet. This compound is [CH3NH3][Co(HCOO)3] with a perovskite-like structure. The A-site [CH3NH3](+) cation strongly distorts the framework, allowing anisotropic magnetic and electric behavior and coupling between them to occur.